Silicon carbide reinforced zirconium based cladding

ABSTRACT

A method for making an improved nuclear fuel cladding tube includes reinforcing a Zr alloy tube by first winding or braiding ceramic yarn directly around the tube to form a ceramic covering, then physically bonding the ceramic covering to the tube by applying a first coating selected from the group consisting of Nb, Nb alloy, Nb oxide, Cr, Cr oxide, Cr alloy, or combinations thereof, by one of a thermal deposition process or a physical deposition process to provide structural support member for the Zr tube, and optionally applying a second coating and optionally applying a third coating by one of a thermal deposition process or a physical deposition process. If the tube softens at 800° C.-1000° C., the structural support tube will reinforce the Zr alloy tube against ballooning and bursting, thereby preventing the release of fission products to the reactor coolant.

RELATED APPLICATIONS

This application claims priority from U.S. Provisional Application Ser.No. 62/698,326 filed Jul. 16, 2018 and incorporated herein by reference.

STATEMENT REGARDING GOVERNMENT RIGHTS

This invention was made with government support under Contract No.DE-NE0008222 awarded by the Department of Energy. The U.S. Governmenthas certain rights in this invention.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present application relates to nuclear fuel claddings, and moreparticularly to zirconium alloy tubes with ceramic coatings.

2. Description of the Prior Art

In a typical nuclear reactor, the reactor core includes a large numberof fuel assemblies, each of which is composed of a plurality ofelongated fuel rods. The fuel rods each contain nuclear fuel fissilematerial, usually in the form of a stack of nuclear fuel pelletssurrounded by a gas, such as He or H₂. The fuel rods have a claddingthat acts as a containment for the fissile material.

A zirconium (Zr) alloy has been used as the cladding on the fuel rods.Exemplary Zr alloys are disclosed in U.S. Pat. Nos. 3,427,222;5,075,075; and 7,139,360, the relevant portions of which areincorporated herein by reference.

Under severe conditions such as “beyond design basis” accidents, metalcladding can react exothermally with steam at over 1093° C. Thesezirconium cladding metals protecting the nuclear fuel may lose strengthduring “a loss of coolant” accident, where reactor temperatures canreach as high as 1204° C., and expand and burst due to internal fissiongases within the fuel rod.

It has been proposed that fuel rod cladding can be coated with materialsto prevent exterior corrosion as disclosed in U.S. Pat. Nos. 9,336,909and 8,971,476, the relevant portions of which are incorporated herein byreference. Coated Zr cladding overcomes one of the major issuesassociated with beyond design basis accidents: excessive oxidation above1200° C. Coating with just chromium (Cr) produces a low melting eutecticbetween Zr and Cr at lower than the 1333° C. temperature because of theother components of the Zr alloy. To get around this issue, an initialniobium (Nb) coating has been proposed.

Even with the coatings, because it is still a metal tube, it stillballoons and bursts at between 800° C. and 1100° C., releasingradioactive fission products to the reactor coolant and allowing coolantto attack the unprotected inside of the tube.

Ceramic type materials have been proposed as cladding material.Ceramic-containing coating materials, such as aluminum (III) oxide(Al₂O₃) and silicon carbide (SiC) have been shown to have desirablesafety properties. Experimental ceramic type materials such as SiCmonolith, fibers and their combinations are taught in U.S. Pat. Nos.6,246,740; 5,391,428; 5,338,576; and 5,182,077, and U.S. PatentApplication Publications 2006/0039524, 2007/0189952; and 2015/0078505,the relevant portions of which are incorporated herein by reference.

Ceramic composites have many desirable properties for use as a nuclearfuel cladding, particularly in “beyond design basis” accidents where,for example, temperatures exceed 1200° C. Use of an inner sleevecomposed of a Zr alloy and an outer sleeve of ceramic fibers has beentried by first making a ceramic sleeve, such as a winding using ceramicfiber tows by braiding or by winding the fiber tows about the outersurface of a form or mandrel and then fitting the winding over the Zralloy tube. It was found that with this approach, there are gaps formedin the spaces between the exterior of the Zr cladding tube and theceramic sleeve and further the ceramic winding can be damaged duringremoval of the mandrel.

Coating the tube and then slipping it into a ceramic sleeve has beentried. However, the formation of a gap 30′ between the ceramic winding14′ and the coated tube 12′, as shown in FIG. 1, results in higher fueltemperatures, especially in high linear heat generation portions of thefuel rod core.

SUMMARY OF THE INVENTION

The following summary is provided to facilitate an understanding of someof the innovative features unique to the embodiments disclosed and isnot intended to be a full description. A full appreciation of thevarious aspects of the embodiments can be gained by taking the entirespecification, claims, abstract and drawings as a whole.

The method described herein provides an improved way of forming nuclearcladding tubes. In various aspects, the method of making a nuclear fuelcladding tube includes covering a zirconium alloy tube with a yarnformed from ceramic fibers by applying the yarn directly onto the tube,applying a first coating to physically bind the ceramic yarn to thetube, and applying a second coating over the first coating. The firstcoating in various aspects is selected from the group consisting of Nb,Nb alloy, Nb oxide, Cr, Cr alloy, Cr oxide, and combinations thereof.The first coating, in various aspects, physically binds the ceramic yarnto the Zr alloy tube, and may fill or substantially fill gaps, if any,between the fibers and between the fibers and the Zr alloy tube. Secondor third optional coatings, in various aspects, may be selected from thegroup consisting of Cr, a Cr alloy, Cr oxide, and combinations thereof.

The tube may be covered by winding or braiding the ceramic yarn aroundthe tube, and preferably by winding or braiding the ceramic yarn tightlyaround the tube such that the entire exterior surface, or substantiallythe entire exterior surface, of the tube is in contact with and coveredby the ceramic yarn. The ceramic covering in various aspects is of asufficient density to provide structural support for the tube attemperatures of 800° C. and above. In various aspects, the ceramic yarnis made from SiC fibers. The spacing between the SiC fibers can be from0 to 2 mm, more preferably from 0.6 to 1.0 mm.

The first and second coatings may be applied by the same or a differentprocess. For example, either the first or second coatings may be appliedby one of a physical vapor deposition process or a thermal depositionprocess. If a thermal deposition process is used for either the first orthe second coating application, it may be one of a cold spray or a hotspray process. If a physical vapor deposition process is used for eitherof the first or the second coating application, it may be one ofevaporation or sputtering, such as cathodic arc vapor deposition,magnetron sputtering deposition, and pulsed laser deposition. Thephysical evaporation deposition process may use a cathodic arc andelectron beam source.

The method described herein produces a nuclear fuel cladding tubecomprised of a zirconium alloy tube, a supporting member comprised of aceramic covering, such as a SiC covering, braided or wound directly ontothe tube and bound to the tube by a first coating selected, for example,from the group consisting of Nb, Nb alloy, Nb-oxide, Cr, Cr alloy, Croxide, and combinations thereof. The cladding tube may optionallycomprise a second coating over the first coating. A second coating maybe selected from the group consisting of Cr, Cr alloys, Cr oxide, andcombinations thereof. The cladding tube may optionally comprise a thirdcoating over the second coating. A third coating also may be selectedfrom the group consisting of Cr, Cr alloys, Cr oxide, and combinationsthereof.

In certain aspects, a SiC covering layer may be between 100 and 600microns in thickness. In certain aspects, the first coating layer may bebetween 1 and 20 microns in thickness. In certain aspects, the secondcoating layer may be between 1 and 50 microns. In certain aspects, theZr tube wall thickness may be between 100 and 1000 microns.

Heretofore, a drawback in using Zr alloy cladding was its potential toballoon and burst at temperatures between 800° C. and 1000° C. Themethod described herein addresses such structural weakness byreinforcing the Zr alloy tube by first winding or braiding ceramic yarnformed for example from SiC fibers, directly around the tube therebyminimizing, and preferably significantly minimizing, and more preferablyeliminating, gaps between the exterior of the tube and the interior ofthe fiber support. The fiber covering is then bonded to the Zr alloytube by means of one or more cold or hot sprayed coatings or coatingsapplied using physical vapor deposition process or a combination of thetwo application methods, providing a structural support member for theZr tube. The SiC covering will provide support to the Zr alloy tube sothat when it softens at 1000° C., the tube will not balloon and burstand release fission products to the reactor coolant.

It should be understood that this disclosure is not limited to theembodiments disclosed in this Summary, and it is intended to covermodifications that are within the spirit and scope of the invention, asdefined by the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The characteristics and advantages of the present disclosure may bebetter understood by reference to the accompanying figures.

FIG. 1 is a section view of a prior art tube with a braided sleeveshowing gaps between the exterior of the tube and the inner side of thefiber windings and some structural deformation of the tube.

FIG. 2 shows braided fibers wound on the exterior of a tube.

FIG. 3 is a schematic illustration of a nuclear cladding tube, such asthe Zr alloy tube described herein.

FIG. 4 is a schematic illustration of the tube of FIG. 3 showing thebraided fibers wound around the exterior of the tube.

FIG. 5 is a schematic illustration of the tube and fibers of FIG. 4 witha first coating added to bind the fibers to the tube.

FIG. 6 is a schematic illustration of the tube of FIG. 5 with a secondand third coating added thereto.

FIG. 7 is a cross-sectional view of the tube of FIG. 5 with a secondcoating added, showing the Zr alloy tube, the ceramic fiber wound aroundthe tube, and the first and second coatings over the fibers. Nuclearfuel pellets are stacked in the cladding tube.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, the singular form of “a”, “an”, and “the” include theplural references unless the context clearly dictates otherwise.

Directional phrases used herein, such as, for example and withoutlimitation, top, bottom, left, right, lower, upper, front, back, andvariations thereof, shall relate to the orientation of the elementsshown in the accompanying drawing and are not limiting upon the claimsunless otherwise expressly stated.

In the present application, including the claims, other than whereotherwise indicated, all numbers expressing quantities, values orcharacteristics are to be understood as being modified in all instancesby the term “about.” Thus, numbers may be read as if preceded by theword “about” even though the term “about” may not expressly appear withthe number. Accordingly, unless indicated to the contrary, any numericalparameters set forth in the following description may vary depending onthe desired properties one seeks to obtain in the compositions andmethods according to the present disclosure. At the very least, and notas an attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter described in thepresent description should at least be construed in light of the numberof reported significant digits and by applying ordinary roundingtechniques.

Any numerical range recited herein is intended to include all sub-rangessubsumed therein. For example, a range of “1 to 10” is intended toinclude all sub-ranges between (and including) the recited minimum valueof 1 and the recited maximum value of 10, that is, having a minimumvalue equal to or greater than 1 and a maximum value of equal to or lessthan 10.

An improved method for manufacturing a composite cladding tube 10 for anuclear fuel rod is described herein. Referring to the Figures, acladding tube 10 produced by the improved method is comprised of azirconium alloy tube 12, a ceramic fiber support member 14 formed frombraided or wound ceramic yarn 16 wound directly onto the exterior 20 ofthe tube 12. The interior side 22 of the covering 14 contactssubstantially the entire exterior 20 of the tube 12, and in variousaspects, covers the entire exterior surface 20 of the tube 12. A firstcoating 24 coats the yarn 16 and fiber covering 14 to physically bindthe fiber covering 14 to the tube 12. To the extent that there are anygaps between yarns 16 or between tows of yarn or between the fibercovering 14 and the tube 12, particles 18 of the first coating 24 fills,or at least substantially fills the gaps sufficiently to provide thedesired structural support for the tube 12. A second coating 26 may, invarious aspects, be applied over the first coating 24. A third coating28, in various aspects, may be applied over the second coating 26. Acompleted cladding tube 10 contains a stack of nuclear fuel pellets 50.

In various aspects, the method may include fabricating a Zr alloy tube12 to a desired length and thickness. In certain aspects, the method mayinclude forming the tube 12 with a wall thickness, for example, of about100 and 1000 microns.

Structural support for the Zr alloy tube 12 is provided by winding orbraiding yarn 16 formed from ceramic fibers over the exterior of thetube 12 to form a ceramic fiber covering 14. Braiding and windingtechniques are well known to those skilled in this area of endeavor.

The ceramic yarn that is wound around the Zr alloy tube 12 is formedfrom small ceramic fibers that are wound into a tow to make the yarn.The yarn is formed into the desired geometry using conventionaltechniques known in the art including, for example, braiding, knitting,weaving, or winding the yarn around the tube 12. See, for example, U.S.Pat. No. 5,391,428. As shown in FIG. 2, the contours of the wrappedfiber yarn 16 may create uneven surfaces and gaps 30 between and amongadjacent sections of yarn.

In various aspects, the ceramic yarn is formed from SiC fibers. The SiCfiber may preferably be a SiC fiber containing primarily Si and C, andsome trace or relatively small amounts of O. Exemplary amounts mayinclude

-   -   Si: 50% to 75% (more preferably 68% to 72%) by weight    -   C: 25% to 60% (more preferably 28% to 32%) by weight    -   O: 0.01% to 14% (more preferably 0.01% to 1%) by weight.

The SiC ceramic covering would utilize SiC in the form of fiber towswith between 500 to 5000 fibers per tow. The thickness of the SiC layerwould be between 100 and 600 microns. The spacing between the SiC fiberscan be from 0 to 2 mm, more preferably from 0.6 to 1.0 mm.

In various aspects, referring to FIGS. 3-6, the Zr alloy tube 12 mayfirst be wound or braided with ceramic yarns 16, formed for example fromSiC fibers in a weave just dense enough to support the tube 12 and notallow ballooning at temperatures above 800° C. Physical vapor depositionor a thermal deposition process may then be used to provide a firstcoating physically bound to the ceramic material and to the spaces orgaps between the ceramic fibers on the Zr tube. The first coating may,in various aspects be made of a first material selected from Nb, Nballoy, Nb oxide, Cr, Cr alloy, Cr oxide, and mixtures of any of theforegoing. A second coating may be applied over the first coating toform a top layer. The second coating is, in various aspects, made of asecond material selected from Cr, Cr oxide, Cr alloy, and mixtures ofany two or more thereof. The second coating layer may be applied by aphysical vapor deposition or a thermal deposition process. In certainaspects, a third coating may be applied over the second coating, inwhich case the third coating rather than the second coating forms thetop layer. The third coating may be made, in various aspects, of a thirdmaterial selected from Cr, Cr oxide, Cr alloy, and mixtures of any twoor more thereof. The third coating layer may be applied by a physicalvapor deposition or a thermal deposition process.

The ceramic fibers, for example, SiC fibers, will provide support to theZr alloy tube 12 so that when it softens at 800° C.-1000° C. it will notballoon and burst and release fission products to the reactor coolant.The first coating 24 both protects the ceramic covering 14 from abrasionby the second coating 26 and forms a protective layer between the Zrtube 12 and the second coating 26 to prevent formation of a low meltingeutectic.

The SiC fiber is much harder (9.2 to 9.3 Mohs) than the Zr alloy (5Mohs) and the preferred materials used to coat the tube; for example, Cr(8.5 Mohs) and Nb (6 Mohs). SiC fibers also have good thermal stabilityand corrosion resistance to greater than 1600° C. but begin to rapidlyoxidize at approximately 1850° C. A second or third layer 26/28 of Crwhich in various aspects forms a layer of Cr₂O₃ outer coating is bothhard and very corrosion resistant to about 2200° C.

Cr and Nb, as used herein, may be pure chromium or pure niobium,respectively, which as used herein, means preferably 100% metallicchromium or niobium, respectively, which may include trace amounts ofunintended impurities that do not serve any metallurgical function. Forexample, pure Cr may contain a few ppm of oxygen. “Cr alloy” or “Nballoy” as used herein refer to alloys with Cr or Nb, respectively, asthe dominant or majority element together with small but reasonableamounts of other elements that serve a specific function. The Cr alloy,for example, may comprise 80% to 99 atom % of chromium. Other element inthe Cr alloy may include at least one chemical element selected fromsilicon, yttrium, aluminum, titanium, niobium, zirconium, and othertransition metal elements. Such elements may be present for example at acontent of 0.1 atomic % to 20 atomic %. Cr oxides as used herein mayinclude Cr₂O₃ and other forms where Cr and O are the dominant elementswith small or trace amounts or unintended impurities of other elements.Nb oxides as used herein may include N₂O₅ and other forms where Nb and Oare the dominant elements with small or trace amounts or unintendedimpurities of other elements.

After the ceramic yarn is wound or braided onto the Zr alloy tube, thefirst coating is applied using, for example, a thermal depositionprocess, such as hot or cold spray, or advantageously, a physical vapordeposition (PVD) process, such as cathodic arc physical vapordeposition, magnetron sputtering, or pulse laser deposition (PLD). Thefirst coating layer 24 will be deposited before the second coating layer26 and may, in certain aspects, be ground and polished before depositionof the second coating layer 26. After the first coating layer 24 isapplied, and optionally ground or polished, the second coating layer 26is applied. The second coating layer 26, like the first may be appliedby a thermal deposition process, such as hot or cold spray, or by aphysical vapor deposition process, and may also be ground and polishedthereafter.

A suitable thermal deposition method, in various aspects, includeseither a hot spray or cold spray methods. In a hot thermal sprayprocess, the coating feedstock material is melted by a heat source or byplasma created by a high frequency arc between an anode and a tungstencathode (i.e. plasma arc spray). This softened liquid or molten materialis then carried by process gas and would be sprayed onto the targetsurface, in this case, the yarn covered tube for application of thefirst coating, or the first coating for application of the secondcoating.

A cold spray method may proceed by delivering a carrier gas to a heaterwhere the carrier gas is heated to a temperature sufficient to maintainthe gas at a desired temperature, for example, from 100° C. to 1200° C.,after expansion of the gas as it passes through a nozzle. In variousaspects, the carrier gas may be pre-heated to a temperature between 200°C. and 1200° C., with a pressure, for example, of 5.0 MPa. In certainaspects, the carrier gas may be pre-heated to a temperature between 200°C. and 1000° C., or in certain aspects, 300° C. and 900° C. and in otheraspects, between 500 C and 800° C. The temperature will depend on theJoule-Thomson cooling coefficient of the particular gas used as thecarrier. Whether or not a gas cools upon expansion or compression whensubjected to pressure changes depends on the value of its Joule-Thomsoncoefficient. For positive Joule-Thomson coefficients, the carrier gascools and must be preheated to prevent excessive cooling which canaffect the performance of the cold spray process. Those skilled in theart can determine the degree of heating using well known calculations toprevent excessive cooling. For example, for N₂ as a carrier gas, if theinlet temperature is 130° C., the Joule-Thomson coefficient is 0.1°C./bar. For the gas to impact the tube at 130° C. if its initialpressure is 10 bar (˜146.9 psia) and the final pressure is 1 bar (˜14.69psia), then the gas needs to be preheated to about 9 bar*0.1° C./bar orabout 0.9 C to about 130.9° C.

For example, the temperature for helium gas as the carrier is preferably450° C. at a pressure of 3.0 to 4.0 MPa, and the temperature fornitrogen as the carrier may be 1100° C. at a pressure of 5.0 MPa, butmay also be 600° C.-800° C. at a pressure of 3.0 to 4.0 MPa. Thoseskilled in the art will recognize that the temperature and pressurevariables may change depending on the type of the equipment used andthat equipment can be modified to adjust the temperature, pressure andvolume parameters.

Suitable carrier gases are those that are inert or are not reactive, andthose that particularly will not react with the particles forming thecoating or the target substrate. Exemplary carrier gases includenitrogen (N₂), hydrogen (H₂), argon (Ar), carbon dioxide (CO₂), andhelium (He).

There is considerable flexibility in regard to the selected carriergases. Mixtures of gases may be used. Selection is driven by bothphysics and economics. For example, lower molecular weight gases providehigher velocities, but the highest velocities should be avoided as theycould lead to a rebound of particles and therefore diminish the numberof deposited particles.

The cold spray process relies on the controlled expansion of the heatedcarrier gas to propel the particles onto the substrate. The particlesimpact the substrate or a previous deposited layer and undergo plasticdeformation through adiabatic shear. Subsequent particle impacts buildup to form the coating. The particles may also be warmed to temperaturesone-third to one-half the melting point of powder expressed in degreesKelvin before entering the flowing carrier gas in order to promotedeformation.

In an exemplary cold spray process, a high pressure gas enters through aconduit to a heater, where heating occurs quickly; substantiallyinstantaneously. When heated to the desired temperature, the gas isdirected to a gun-like instrument. Particles of the desired coatingmaterial, such as Cr, Cr alloy, Cr oxide, Nb, Nb alloy, Nb oxides, ormixtures thereof for the first coating, or Cr, Cr alloys, Cr oxides, ormixtures thereof for the second or third coating, are held in a hopper,and are released and directed to a gun where they are forced through anozzle towards the target substrate by a pressurized gas jet. Thesprayed particles are deposited onto target surface to form a coatingcomprised of the desired particles.

Several physical vapor deposition (PVD) processes are known in the artfor depositing thin layers of materials, such as particles, to asubstrate and may be used to apply one or both of the first and secondcoating layers. PVD may be characterized as a collective set of vacuumdeposition techniques consisting of three fundamental steps: (1)vaporization of the material from a solid source assisted by hightemperature vacuum or gaseous plasma; (2) transportation of the vapor invacuum or partial vacuum to the substrate surface; and, (3) condensationonto the substrate to generate thin films.

The most common of the PVD coating processes are evaporation (typicallyusing cathodic arc or electron beam sources), and sputtering (usingmagnetic enhanced sources or “magnetrons”, cylindrical or hollow cathodesources). All of these processes occur in vacuum at working pressure(typically 10-2 to 10-4 mbar) and generally involve bombardment of thesubstrate to be coated with energetic positively charged ions during thecoating process to promote high density. Additionally, reactive gasesmay be introduced into the vacuum chamber during metal deposition tocreate various compound coating compositions. The result is a verystrong bond between the coating and the substrate and tailored physicaland properties of the deposited layer.

Cathodic arc vapor deposition involves a source material and a substrateto be coated placed in an evacuated deposition chamber. The chambercontains only a relatively small amount of gas. The negative lead of adirect current (DC) power supply is attached to the source material (the“cathode”) and the positive lead is attached to an anode. In many cases,the positive lead is attached to the deposition chamber, thereby makingthe chamber the anode. The electric arc is used to vaporize materialfrom the cathode target. The vaporized material then condenses on thesubstrate, forming the desired layer.

Magnetron Sputtering is a plasma vapor deposition process in which aplasma is created and positively charged ions from the plasma areaccelerated by an electrical field superimposed on the negativelycharged electrode or “target”. The positive ions are accelerated bypotentials ranging from a few hundred to a few thousand electron voltsand strike the negative electrode with sufficient force to dislodge andeject atoms from the target. These atoms will be ejected in a typicalline-of-sight cosine distribution from the face of the target and willcondense on surfaces that are placed in proximity to the magnetronsputtering cathode.

Pulsed laser deposition (PLD) is a physical vapor deposition techniquewhere a high-power pulsed laser beam is focused inside a vacuum chamberto strike a target of the material that is to be deposited. Thismaterial is vaporized from the target (in a plasma plume) which depositsit as a thin film on a substrate. The process of PLD can generally bedivided into five stages: (1) laser absorption on the target surface;(2) laser ablation of the target material and creation of a plasma; (3)dynamic of the plasma; (4) deposition of the ablation material on thesubstrate; and (5) nucleation and growth of the film on the substratesurface.

Following the deposition of either or both of the first and secondcoating layers 24, 26, the method may further include annealing thelayers. Annealing modifies mechanical properties and microstructure ofthe coatings. Annealing involves heating the coating in the temperaturerange of 200° C. to 800° C., and preferably between 350° C. to 550° C.It relieves the stresses in the coating and imparts ductility to thecoating which is necessary to sustain internal pressure in the cladding.As the tube bulges, the coating should also be able to bulge. Anotherimportant effect of annealing is the deformed grains formed for exampleduring cold spray process get recrystallized to form fine sub-micronsized equiaxed grains which may be beneficial for isotropic propertiesand radiation damage resistance.

The coated layers may also be ground, buffed, polished, or treated byother known techniques to achieve a smoother surface finish.

The first coating layer formed from Cr, a Cr alloy, Cr oxide, Nb, Nballoy, Nb oxide, or mixtures thereof may be between 1 and 20 microns.The second or third coating layers formed from Cr, Cr alloy, and/or Croxide layer and mixtures thereof may be between 1 and 50 microns.Because the Zr alloy tube is supported by the SiC support layer, itswall thickness can be between 100 and 1000 microns.

The proposed approach combines the strong points of ceramic,particularly SiC ceramic, and coated cladding to provide a low costapproach to making a corrosion resistant tube that does not balloon andburst.

By winding, for example, SiC fiber yarns 16 directly around the tube 12to form a support covering 14, there is a significant reduction in airgaps between the tube 12 and the ceramic fiber covering 14 that istypically experienced when the fiber sleeve is formed first and thenplaced over the tube. It is estimated that this approach would reducethe cost of a cladding by about 25% while retaining the benefits of bothZr alloy and ceramic claddings. The lower cost is due to the eliminationof the manufacturing steps for the ceramic composite except for windingwhich are relatively small and to the reduction in the amount of ceramicmaterial needed as compared to an all ceramic composite tube. Thematerial reduction is possible because the Zr alloy tube 12 providesmost of the structural support and hermeticity, while the ceramiccovering 14 supports the Zr tube 12 at high temperatures.

All patents, patent applications, publications, or other disclosurematerial mentioned herein, are hereby incorporated by reference in theirentirety as if each individual reference was expressly incorporated byreference respectively. All references, and any material, or portionthereof, that are said to be incorporated by reference herein areincorporated herein only to the extent that the incorporated materialdoes not conflict with existing definitions, statements, or otherdisclosure material set forth in this disclosure. As such, and to theextent necessary, the disclosure as set forth herein supersedes anyconflicting material incorporated herein by reference and the disclosureexpressly set forth in the present application controls.

The present invention has been described with reference to variousexemplary and illustrative embodiments. The embodiments described hereinare understood as providing illustrative features of varying detail ofvarious embodiments of the disclosed invention; and therefore, unlessotherwise specified, it is to be understood that, to the extentpossible, one or more features, elements, components, constituents,ingredients, structures, modules, and/or aspects of the disclosedembodiments may be combined, separated, interchanged, and/or rearrangedwith or relative to one or more other features, elements, components,constituents, ingredients, structures, modules, and/or aspects of thedisclosed embodiments without departing from the scope of the disclosedinvention. Accordingly, it will be recognized by persons having ordinaryskill in the art that various substitutions, modifications orcombinations of any of the exemplary embodiments may be made withoutdeparting from the scope of the invention. In addition, persons skilledin the art will recognize, or be able to ascertain using no more thanroutine experimentation, many equivalents to the various embodiments ofthe invention described herein upon review of this specification. Thus,the invention is not limited by the description of the variousembodiments, but rather by the claims.

What is claimed is:
 1. A method of making a nuclear fuel cladding tubecomprising: covering a zirconium alloy tube with ceramic fiber yarn byapplying the yarn directly onto the tube; and applying a first coatingto bind the ceramic fiber yarn to the tube.
 2. The method recited inclaim 1 wherein the first coating is made of a material selected fromthe group consisting of Nb, Nb alloy, Nb oxide, Cr, Cr alloy, Cr oxide,and combinations thereof.
 3. The method recited in claim 1 wherein thefirst coating is applied by one of a physical vapor deposition processor a thermal deposition process.
 4. The method recited in claim 3wherein the thermal deposition process is one of a cold spray or a hotspray process.
 5. The method recited in claim 3 wherein the physicalvapor deposition process selected from the group consisting ofevaporation and sputtering.
 6. The method recited in claim 3 wherein thephysical vapor deposition process is selected from the group consistingof cathodic arc vapor deposition, magnetron sputtering deposition, andpulsed laser deposition.
 8. The method recited in claim 1 wherein thefirst coating forms a layer of between 1 and 20 microns in thickness. 8.The method recited in claim 1 further comprising applying a secondcoating to cover the first coating.
 9. The method recited in claim 8wherein the second coating is made of a material selected from the groupconsisting of Cr, a Cr alloy, Cr oxide, and combinations thereof. 10.The method recited in claim 8 wherein the second coating forms a layerof between 1 and 50 microns.
 11. The method recited in claim 8 whereinthe second coating is applied by one of a physical vapor depositionprocess or a thermal deposition process.
 12. The method recited in claim11 wherein the thermal deposition process is one of a cold spray or ahot spray process.
 13. The method recited in claim 11 wherein thephysical vapor deposition process selected from the group consisting ofevaporation and sputtering.
 14. The method recited in claim 11 whereinthe physical vapor deposition process is selected from the groupconsisting of cathodic arc vapor deposition, magnetron sputteringdeposition, and pulsed laser deposition.
 15. The method recited in claim11 wherein the first and second coatings are each formed by a thermaldeposition process.
 16. The method recited in claim 8 further comprisingapplying a third coating to cover the second coating.
 17. The methodrecited in claim 16 wherein the third coating is made of a materialselected from the group consisting of Cr, a Cr alloy, Cr oxide, andcombinations thereof.
 18. The method recited in claim 16 wherein thethird coating is applied by one of a physical vapor deposition processor a thermal deposition process.
 19. The method recited in claim 1wherein the ceramic fiber yarn is of a sufficient density to providestructural support for the tube at temperatures of 800° C. and above.20. The method recited in claim 1 wherein the ceramic fiber yarn forms alayer of between 100 and 600 microns in thickness.
 21. The methodrecited in claim 1 wherein the Zr tube has a wall thickness of between100 and 1000 microns.
 22. The method recited in claim 1 wherein applyingthe ceramic yarn directly onto the tube comprises one of braiding orwinding the yarn around the tube.
 23. The method recited in claim 1wherein the ceramic fiber yarn is made of SiC fibers.
 24. A nuclear fuelcladding tube comprising: a zirconium alloy tube; and, a structuralsupport member comprised of a ceramic covering applied directly onto thetube and a first coating layer binding the ceramic covering to the tube.25. The cladding tube recited in claim 24 wherein the first coatinglayer is formed from a first material selected from the group consistingof Nb, Nb alloy, Nb-oxide, Cr, Cr alloy, Cr oxide, and combinationsthereof.
 26. The cladding tube recited in claim 24 further comprising atleast a second coating layer over the first coating.
 27. The claddingtube recited in claim 26 wherein the at least second coating layer isformed from a material selected from the group consisting of Cr, Cralloys, Cr oxide, and combinations thereof.
 28. The cladding tuberecited in claim 26 wherein the at least second coating layer is between1 and 50 microns.
 29. The cladding tube recited in claim 24 wherein theceramic covering is formed from yarn made of SiC fibers applied by oneof braiding or winding onto the tube, the covering being between 100 and600 microns in thickness.
 30. The cladding tube recited in claim 24wherein the first coating layer is between 1 and 20 microns inthickness.
 31. The cladding tube recited in claim 24 wherein the Zr tubewall thickness is between 100 and 1000 microns.
 32. A nuclear fuelcladding tube comprising: a zirconium alloy tube having a wall thicknessbetween 100 and 1000 microns; a structural support member comprised of aSiC braided yarn covering applied directly onto the tube and a firstcoating layer binding the covering to the tube, the first coating madeof a first material selected from the group consisting of Nb, Nb alloy,Nb oxide, and combinations thereof; and, at least one second coatinglayer over the first coating, the second coating made of a secondmaterial selected from the group consisting of Cr, Cr alloys, Cr oxide,and combinations thereof.
 33. A method of making a nuclear fuel claddingtube comprising: covering a zirconium alloy tube with SiC fiber yarn bywinding the yarn directly onto the tube, the covering being between 100and 600 microns in thickness and having a density sufficient to providestructural support for the tube at temperatures of 800° C. and above;applying a first coating to a thickness of between 1 and 20 micronsusing a physical vapor deposition process, the first coating being madeof a first material selected from the group consisting of Nb, Nb alloy,Nb oxide, Cr, Cr alloy, Cr oxide, and combinations thereof to physicallybind the yarn to the tube; and, applying at least one second coating toa thickness of between 1 and 50 microns using a thermal depositionprocess, the at least one second coating being made of a second materialselected from the group consisting of Cr, Cr alloys, Cr oxide, andcombinations thereof, to cover the first coating.